PL213085B1 - New derivative of (+)-3-carene - Google Patents
New derivative of (+)-3-careneInfo
- Publication number
- PL213085B1 PL213085B1 PL391220A PL39122010A PL213085B1 PL 213085 B1 PL213085 B1 PL 213085B1 PL 391220 A PL391220 A PL 391220A PL 39122010 A PL39122010 A PL 39122010A PL 213085 B1 PL213085 B1 PL 213085B1
- Authority
- PL
- Poland
- Prior art keywords
- carene
- new derivative
- derivative
- new
- trimethylbicyclo
- Prior art date
Links
- 150000000015 (+)-car-3-ene derivatives Chemical class 0.000 title 1
- -1 Hept-4-en-3-yl Chemical group 0.000 claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011046 carnelian Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 2
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000779819 Syncarpia glomulifera Species 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229930007744 linalool Natural products 0.000 description 2
- 239000001739 pinus spp. Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229940036248 turpentine Drugs 0.000 description 2
- BQOFWKZOCNGFEC-DTWKUNHWSA-N (-)-Delta(3)-carene Chemical compound C1C(C)=CC[C@@H]2C(C)(C)[C@H]12 BQOFWKZOCNGFEC-DTWKUNHWSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- RQOKOSIDJPMJPY-QZPOHEPASA-N CC=1[C@@H](CC2C([C@H]2C=1)(C)C)C(C)(C=C)O Chemical compound CC=1[C@@H](CC2C([C@H]2C=1)(C)C)C(C)(C=C)O RQOKOSIDJPMJPY-QZPOHEPASA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 235000008124 Picea excelsa Nutrition 0.000 description 1
- 244000193463 Picea excelsa Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000008582 Pinus sylvestris Nutrition 0.000 description 1
- 241000218626 Pinus sylvestris Species 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest nowa pochodna (+)-3-karenu, charakteryzująca się zapachem podobnym do linalolu, przeznaczona do wytwarzania kompozycji zapachowych.The subject of the invention is a new (+) - 3-carnelian derivative, characterized by a linalool-like odor, intended for the production of fragrances.
3-Karen jest węglowodorem terpenowym pozyskiwanym z terpentyn sosnowych, w Polsce z terpentyn sosny zwyczajnej Pinus silvestris, zawierających około 40% 3-karenu.3-Karen is a terpene hydrocarbon obtained from pine turpentine, in Poland from Pinus silvestris Scots pine turpentine, containing about 40% of 3-carnelian.
Znana jest pochodna 3-karenu stanowiąca produkt jego acetylacji, tj. 3-acetylokaren-4, stanowiąca związek zapachowy.The derivative of 3-carne is known to be the product of its acetylation, ie 3-acetylcarene-4, which is a fragrance.
Przedmiotem wynalazku jest nowa pochodna (+)-3-karenu, którą stanowi 2-((3R,6S)-4,7,7-trimetylobicyklo[4.1.0.]hept-4-en-3-ylo)-3-buten-2-ol, o wzorze 1:The subject of the invention is a new (+) - 3-kararene derivative, which is 2 - ((3R, 6S) -4,7,7-trimethylbicyclo [4.1.0.] Hept-4-en-3-yl) -3- buten-2-ol, Formula 1:
Nowa pochodna (+)-3-karenu charakteryzuje się intensywnym, trwałym kwiatowo-drzewnym, z odcieniem tytoniowym zapachem, podobnym nieco do zapachu linalolu, przy czym trwałość jej zapachu jest około 8-krotnie większa od trwałości zapachu linalolu. Nowa pochodna znajduje zastosowanie do tworzenia środkowej i dolnej nuty kompozycji zapachowych.The new derivative of (+) - 3-carnelian is characterized by an intense, persistent floral-woody, with a tobacco flavor, somewhat similar to the smell of linalool, with the durability of its smell being about 8 times greater than that of linalool. The new derivative is used to create the middle and bottom notes of fragrance compositions.
Właściwości fizyko-chemiczne i spektralne nowego związku są następujące:The physico-chemical and spectral properties of the new compound are as follows:
[a]D24 = + 203,22 (chloroform, c = 2).[a] D 24 = + 203.22 (chloroform, c = 2).
IR (cm-1): 3346, 2974, 2937, 2876, 1642, 1452, 1373, 1092, 1014, 996, 916, 831.IR (cm -1 ): 3346, 2974, 2937, 2876, 1642, 1452, 1373, 1092, 1014, 996, 916, 831.
MS (m/z): 206 (M, 1), 173 (3), 136 (9), 135 (10),119 (11), 105 (8), 93 (100), 91 (19), 71 (24), 43 (47).MS (m / z): 206 (M, 1), 173 (3), 136 (9), 135 (10), 119 (11), 105 (8), 93 (100), 91 (19), 71 (24), 43 (47).
1HNMR, (δ, CDCl3): 6,09 (dd, J = 17,25 i 10,5 Hz, 1H), 5,65 (m, 1H), 5,31 (dd, J = 17,25 i 1,5 1 HNMR, (δ, CDCl3): 6.09 (dd, J = 17.25 and 10.5 Hz, 1H), 5.65 (m, 1H), 5.31 (dd, J = 17.25 and 1.5
Hz, 1H), 5,05 (dd, J = 10,5 i 1,5 Hz, 1H), 1,79 (s, 3H), 1,44 (s, 3H), 1,10 (s, 3H), 0,90 (s, 3H).Hz, 1H), 5.05 (dd, J = 10.5 and 1.5 Hz, 1H), 1.79 (s, 3H), 1.44 (s, 3H), 1.10 (s, 3H ), 0.90 (s, 3H).
13C NMR (δ, CDCl3): 146,11, 137,80, 124,13, 110,78, 76,23, 47,87, 27,55, 26,16, 25,80, 25,16, 24,49, 21,83, 19,26, 14,80. 13 C NMR (δ, CDCl3): 146.11, 137.80, 124.13, 110.78, 76.23, 47.87, 27.55, 26.16, 25.80, 25.16, 24 , 49, 21.83, 19.26, 14.80.
Nowy związek, 2-((3R,6S)-4,7,7-trimetylobicyklo[4.1.0]hept-4-en-3-ylo)-3-buten-2-ol o wzorze 1, otrzymuje się z 3-acetylokarenu-4 o wzorze 2:The new compound, 2 - ((3R, 6S) -4,7,7-trimethylbicyclo [4.1.0] hept-4-en-3-yl) -3-buten-2-ol of formula 1, is obtained from 3 -acetylcarene-4 of formula 2:
w drodze reakcji tego ketonu z chlorkiem lub bromkiem winylomagnezowym w środowisku tetrahydrofuranu w temperaturze około 40°C w czasie do 3 godzin.by reacting this ketone with vinylmagnesium chloride or bromide in tetrahydrofuran at a temperature of about 40 ° C for up to 3 hours.
PL 213 085 B1PL 213 085 B1
Otrzymany w wyniku tej reakcji surowy produkt, po wyodrębnieniu ze środowiska reakcji, oczyszcza się w drodze destylacji pod zmniejszonym ciśnieniem (94-98°C/0,013 kPa). Z otrzymanej w wyniku destylacji mieszaniny dwóch diastereoizomerów, o proporcji izomerów 1:4, wyizolowuje się izomer główny -2-((3R,6S)-4,7,7-trimetylobicyklo[4.1.0]hept-4-en-3-ylo)-3-buten-2-ol za pomocą chromatografii kolumnowej (silikażel, heksan/octan etylu). Wyizolowany izomer charakteryzuje się wysoką czystością chromatograficzną.The crude product obtained in this reaction, after isolation from the reaction medium, is purified by distillation under reduced pressure (94-98 ° C / 0.013 kPa). The major isomer -2 - ((3R, 6S) -4,7,7-trimethylbicyclo [4.1.0] hept-4-en-3- is isolated from the mixture of two diastereoisomers obtained by distillation with an isomer ratio of 1: 4. yl) -3-buten-2-ol by column chromatography (silica gel, hexane / ethyl acetate). The isolated isomer is characterized by high chromatographic purity.
Przedmiot wynalazku ilustruje poniższy przykład.The following example illustrates the subject of the invention.
P r z y k ł a d 3 Example 3
W kolbie umieszczono 36 cm3 (0,036 mola) bromku winylomagnezowego w postaci roztworu w tetrahydrofuranie i w trakcie mieszania wkroplono 5 g (0,028 mola) 3-acetylokarenu-4 w postaci 3 roztworu w 10 cm3 tetrahydrofuranu w temperaturze 25-30°C. Następnie, kontynuowano mieszanie 3 w temperaturze 40°C w czasie 3 godzin. Po tym czasie dodano do kolby wody oraz 50 cm3 nasycone3 go roztworu wodnego chlorku amonowego i ekstrahowano produkt 3 porcjami po 20 cm3 toluenu. Surowy produkt (6,05 g) oczyszczono w drodze destylacji pod zmniejszonym ciśnieniem otrzymując 4,8 g (wydajność 83%) mieszaniny dwóch diastereoizomerów, o temperaturze wrzenia 94-98°C/0,013 kPa, o proporcji izomerów równej 1:4. Izomer główny - 2-((3R,6S)-4,7,7-trimetylobicyklo[4.1.0]hept-4-en-3-ylo)-3-buten-2-ol wyodrębniono za pomocą chromatografii kolumnowej (silikażel, heksan/octan etylu). Charakteryzował się czystością chromatograficzną 98% oraz podanymi wyżej właściwościami fizykochemicznymi oraz spektralnymi.The flask was placed 36 cm 3 (0.036 mol) of vinyl bromide as a solution in tetrahydrofuran and added dropwise with stirring 5 g (0.028 mol) of 3-acetylokarenu-4 in the form of a solution of 3 in 10 cm 3 of tetrahydrofuran at 25-30 ° C. Then, the stirring was continued for 3 at 40 ° C for 3 hours. After this time, water was added to the flask and 50 cm 3 of saturated aqueous solution of 3 go ammonium chloride and the product was extracted 3 times with 20 cm 3 of toluene. The crude product (6.05 g) was purified by distillation under reduced pressure to give 4.8 g (83% yield) of a mixture of the two diastereoisomers, bp 94-98 ° C / 0.013 kPa, with an isomer ratio of 1: 4. The major isomer - 2 - ((3R, 6S) -4,7,7-trimethylbicyclo [4.1.0] hept-4-en-3-yl) -3-buten-2-ol was isolated by column chromatography (silica gel, hexane / ethyl acetate). It was characterized by a chromatographic purity of 98% and the above-mentioned physicochemical and spectral properties.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL391220A PL213085B1 (en) | 2010-05-14 | 2010-05-14 | New derivative of (+)-3-carene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL391220A PL213085B1 (en) | 2010-05-14 | 2010-05-14 | New derivative of (+)-3-carene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL213085B1 true PL213085B1 (en) | 2013-01-31 |
Family
ID=47624900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL391220A PL213085B1 (en) | 2010-05-14 | 2010-05-14 | New derivative of (+)-3-carene |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL213085B1 (en) |
-
2010
- 2010-05-14 PL PL391220A patent/PL213085B1/en not_active IP Right Cessation
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MX2010011589A (en) | Novel pyran derivatives, their preparation and use thereof in perfumery. | |
| Nomoto et al. | Synthesis of selenium compounds by free radical addition based on visible-light-activated Se-Se bond cleavage | |
| CN107250090A (en) | Method for preparing 1-[(1R,4R/S,8S)-10,10-dimethyl-7-methylene-4-bicyclo[6.2.0]decyl]ethanone | |
| MX395501B (en) | PROCESS FOR THE PREPARATION OF 2,3-UNSATURATED ALCOHOLS. | |
| JP2015511234A (en) | Aldehydes as perfuming ingredients | |
| Tanino et al. | Synthesis of alicyclic esters via an intramolecular conjugate addition reaction. New method for generating (Z)-vinylcopper species from 1, 1-dibromoalkenes | |
| US10040775B2 (en) | Synthesis of chirally enriched 2,4-disubstituted tetrahydropyran-4-ol and its derivatives | |
| PL213085B1 (en) | New derivative of (+)-3-carene | |
| Brel | Synthesis of new pentafluorosulfanylacrylates (F5SCHCHCHO, F5SCHCHCN, F5SCHCHCOOCH3) and use of them as dienophiles in Diels-Alder reaction | |
| CN111448299B (en) | Odorants and compositions containing odorants | |
| JPH06305999A (en) | Odor adsorbent composition | |
| CN102083781A (en) | Methods for preparing aldehydes by self-aldol condensation | |
| Deng et al. | DMP-mediated one-pot oxidative olefination of silyl ethers | |
| JP6751514B2 (en) | Tetrafluorosulfanylpyridine | |
| Šiška et al. | Synthesis and olfactory properties of unnatural derivatives of lilac aldehydes | |
| Chakraborty et al. | A radical mediated approach to the stereoselective formal total synthesis of (+)-Sch 642305 | |
| JP6866291B2 (en) | 2-octylcyclopropyl-1-carboxylic acid and its isomers, and their use | |
| CN103980102A (en) | Synthesis of 2,4-dihydroxy-5-methyl acetophenone and derivative thereof and application of 2,4-dihydroxy-5-methyl acetophenone and derivative thereof as bactericides | |
| WO2014064716A1 (en) | (5h)-1 -benzopyran-5-one derivatives and formulations for perfumery and flavor applications | |
| Lujan-Montelongo et al. | An efficient synthesis of (+/-)-xanthorrhizol: One pot decyanation and demethylation | |
| JP4786267B2 (en) | Method for producing lactone and use of produced lactone as aromatic substance | |
| PL227380B1 (en) | Carene-tetrahydropiran derivative | |
| US9296675B2 (en) | Compound having cyclopropane ring, and flavor and/or fragrance composition containing same | |
| PL221614B1 (en) | Carene-tetrahydrofuran derivative | |
| PL224652B1 (en) | Tetrahydrofuranyl derivative of citronellol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LICE | Declarations of willingness to grant licence |
Effective date: 20120918 |
|
| LAPS | Decisions on the lapse of the protection rights |
Effective date: 20130514 |